CN1636974A - Process for producing sulfinate with low content exogenous salt - Google Patents
Process for producing sulfinate with low content exogenous salt Download PDFInfo
- Publication number
- CN1636974A CN1636974A CN 200410091648 CN200410091648A CN1636974A CN 1636974 A CN1636974 A CN 1636974A CN 200410091648 CN200410091648 CN 200410091648 CN 200410091648 A CN200410091648 A CN 200410091648A CN 1636974 A CN1636974 A CN 1636974A
- Authority
- CN
- China
- Prior art keywords
- salt
- sulfinate
- hyposulfite
- exogenous
- carbonyl compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C313/02—Sulfinic acids; Derivatives thereof
- C07C313/04—Sulfinic acids; Esters thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the method for manufacturing sulfinate with few unnecessary salt comprising reduction of dithionite of alkali metal, alkali earth metal or ammonium by using a carbonyl compound or an imine at pH>6 in manufacturing the sulfinate. The Moore ratio of the dithionite and carbonyl or imine compound is selected preferably in the range of 0.75-1.3. The method provides sulfinate salt product with low content of extraneous salt which can be further removed, if necessary. The method is expecially used for preparing hydroxymethyl sulfonate.
Description
Invention field
The present invention relates to a kind ofly by in pH＞6 time, use the hyposulfite of carbonyl compound or group with imine moiety reducine metal or alkaline-earth metal or ammonium and prepare the method for-sulfinate with low levels exogenous salt.Keep particular concentration ratio between the reactant, can obtain having the product of low levels exogenous salt, and exogenous salt can be removed easily by ordinary method further.
Background technology
-sulfinate is widely used in the industry as reductive agent and as free radical generating agent.For example dye and take off and dye (dye-stripping) operation, and polyaddition reaction.
-sulfinate normally prepares by hyposulfite in the presence of alkali and aldehyde reaction.But known preparation method has such shortcoming: the-sulfinate solution that obtains contains the material that forms in the preparation process.Usually, these solution are just sold without further processing, and in this case, the action intensity by unit mass of product is lower.Generally can remove by product, but expense is big and effort.Owing to the salt that forms makes that the cost of production and Product transport is very high.
For example, when using the zinc powder method (to use zinc, through zinc dithionite intermediate reduction SO
2And subsequently with aldehyde reaction) preparation is during-sulfinate, zinc oxide and zinc hydroxide prepare together.They must be separated from product solution, this is the big and effort of expense, because influenced the economy of whole preparation method usually for the low market requirement of co-product.And the product solution of Huo Deing always contains zine ion as impurity in the method, can have a negative impact when using described-sulfinate product, and this is normally undesirable.
In addition, SO
2Can electrolysis be converted into hyposulfite.At this moment, at mixture that co-production is come out or in isolated hyposulfite, do not have zine ion.Zinc salt is difficult to usually by removing by filter, and this causes zinc salt to be difficult to separate in the process of separating obtained-sulfinate from hyposulfite.
-sulfinate can directly prepare by V-Brite B and aldehyde and alkali reaction.The main by product that forms is sulphite and sulfonate, and they can reduce the action intensity by unit mass of product equally, and must separatedly go out.The economic means that is used for the enrichment-sulfinate and removes exogenous salt is not seen description so far in the literature.
Prepare the existing description of-sulfinate by adding aldehyde gradually by V-Brite B and NaOH, referring to for example Mulliez, Tetrahedron 49,12,2469-2476 page or leaf (1993).About the composition of products therefrom mixture, there is not evidence to demonstrate the ratio of-sulfinate/sulphite and sulfonate.Also not about the description of the hydroxymethanesulfinate of preparation in this manner.In addition, the hyposulfite of use are commercially available high-purity-grades.
Up to now, and do not know that in product mixtures effectively the economic means of enrichment-sulfinate can be obtained by the method for prior art.Hyposulfite by method for preparing have contained a high proportion of impurity.These impurity will enter the follow-up reactions steps single step reaction of going forward side by side.Knownly be enriched in specific-sulfinate in the mixture that makes, referring to US6211400 by adding the polar water solubleness organic solvent.But after enrichment, the-sulfinate content in the product is still very low, is usually less than 80%.-sulfinate loss in the purification process process is also undeclared.
Summary of the invention
Still need from sulfurous gas or hyposulfite, to obtain the method for-sulfinate.This will finish under the situation that does not produce a large amount of exogenous salts.The content of the exogenous salt of Chan Shenging is preferably so low inevitably, makes to make the purifying of gained-sulfinate product and removing of exogenous salt reach the purity grade that meets the expectation of the highest market by using ordinary method.The amount of the sulfonate that more especially, makes should be low.
This purpose can realize by the method for preparing the-sulfinate with low levels exogenous salt with the hyposulfite of carbonyl compound or imines reducine metal or alkaline-earth metal or ammonium in pH＞6 time.
Implement preferred version of the present invention
Reaction of the present invention provides the method for preparing-sulfinate with high yield and selectivity, has greatly suppressed the formation of undesirable by product.Therefore, except valuable product (-sulfinate), the-sulfinate product that obtains only contains a small amount of external product, especially exogenous salt.
Being achieved at high proportion of valuable product and exogenous salt.Gained-sulfinate product has the higher action intensity by unit mass.
" exogenous salt " herein is meant the undesirable salt for preparing together with the-sulfinate principal product.They are sulphite on the one hand, and this is the inevitable stoichiometry product of hyposulfite of the present invention and aldehyde reaction.The beat all advantage of the inventive method is that sulphite forms with stoichiometry, and separate easily is gone out.On the other hand, term " exogenous salt " also comprise form by side reaction or be present in salt in the hyposulfite reactant (preparation process that generally comes from hyposulfite).
The mol ratio of hyposulfite and carbonyl or group with imine moiety is at 0.75: 1.3, in the scope of preferred 0.95-1.05, especially 0.99-1.02.Reactant accurate measurement each other obtains favourable result.
The pH of solution＞6 are preferably in the scope of 8-13, especially in the scope of 9-11.
Generally oxyhydroxide by adding basic metal or alkaline-earth metal or nitrogen base are set to pH and meet the value that the present invention requires.The example of described oxyhydroxide comprises NaOH, KOH, Ca (OH)
2, Mg (OH)
2, Ba (OH)
2Useful nitrogen base is ammonium salt unsubstituted or that replaced by alkyl, alkaryl, aryl and aralkyl, for example tetramethyl ammonium or tetraethyl-ammonium salt.The nitrogen base that is fit to also comprises nitrogen-containing heterocycle compound, for example imidazoline salt or pyridinium salt.The preferred NaOH that uses.
Hyposulfite use with the form of sodium salt usually.Perhaps, also can use other an alkali metal salt hydrosulfurous or alkaline earth salt or ammonium salt.
Hyposulfite can also be with the form of zinc salt (by reduction reaction, by SO
2Obtain with zinc) exist.Hyposulfite preferably do not contain zinc salt.
The inventive method can be undertaken by the hyposulfite that use isolating respective salt, and this moment, salt was purified, perhaps can contain impurity.The inventive method also can be carried out with the form of integrated operation, wherein SO
2Or sulphite is converted into hyposulfite at first, need not subsequently to separate, and hyposulfite are converted into-sulfinate of the present invention immediately.
In the method, SO
2Or sulphite is for example by zinc or electrolytic reduction.The preferred electrolytic reduction reaction of the present invention.
After measured, electrolytic SODIUM HYDROSULPHITE salts solution like this can be used for method of the present invention, because making, this reaction arrangement no longer forms undesirable exogenous salt, and the salt that produces in the hyposulfite preparation process, mainly be sulphite, can easily separate with the exogenous salt of the inventive method.Therefore do not need the purifying hyposulfite.
The gained-sulfinate can be with basic metal, alkaline-earth metal or ammonium salt, and the form of particular certain cancers obtains.
Useful carbonyl compound generally comprises all aldehyde and ketone, is not only aliphatic series and aromatics, also comprise single-with many-functional.Example comprises formaldehyde, acetaldehyde, acetone, pyruvic alcohol, pimelinketone, adipoin, oxalic dialdehyde and Glyoxylic acid hydrate.Preferred formaldehyde.
Imines is to obtain by containing the amine that can extract hydrogen atom and the reaction of aldehyde and ketone.Generally speaking, all imines all are applicable to method of the present invention.Preferably by NH
3The deutero-imines.Especially preferably by formaldehyde and NH
3, methylamine, ethamine, thanomin or quadrol preparation imines, and the BASF name of selling is called the imines of Cyclanon Eco.
Method of the present invention especially can be used for preparing hydroxymethanesulfinate and salt thereof.At this, passed through SO before also being preferred for
2Or the hyposulfite of the electrolytic reduction of sulphite preparation.
Separation is carried out in a conventional manner, for example by selective precipitation, separate under preferred electrodialysis of electrical gradient or electrophoretic influence, perhaps separates for example infiltration, nanofiltration, reverse osmosis or specific ion exchanger under the influence of pressure gradient.
Selective precipitation is generally undertaken by adding the polar water solubleness organic solvent.Example comprises ketone, alcohol, aldehyde, acid amides, sulfoxide, water-soluble cyclic ethers and water-soluble nitrogen heterocyclic ring.
The example of the alcohol that is fit to comprises C
1-C
4Alcohol, glycol, glycerine.The example of the cyclic ethers that is fit to comprises tetrahydrofuran THF with diox.The example of the nitrogen-containing heterocycle compound that is fit to is N-Methyl pyrrolidone (NMP).Other solvent that is fit to is methyl-sulphoxide (DMSO) and dimethyl formamide (DMF).
The preferred alcohol that adds.Most preferably being used for sedimentary solvent is methyl alcohol, ethanol and Virahol.
Use conventional filtration method well known by persons skilled in the art to remove sedimentary exogenous salt.Can under normal atmosphere or elevated pressure, filter.
The method that another kind is removed exogenous salt is electrodialysis.Electrodialytic method is well known by persons skilled in the art.This method can be disconnected from each other with the salt with different electric charges, uses electrical film to carry out usually.Especially when having different electric charge with exogenous salt, uses substrate electrodialysis in the methods of the invention, for example under the situation of sulphite/hydroxymethanesulfinate.Can carry out method of the present invention makes product and exogenous salt have different electric charges.For example, react and make that the exogenous salt that forms in the building-up process of hydroxymethanesulfinate mainly is a sulphite.
The method that another kind is removed exogenous salt is under the influence of pressure gradient, for example infiltration, reverse osmosis, nanofiltration or selectivity ion-exchange.
Method of the present invention is so to have selectivity, makes the exogenous salt (not containing heavy metal and organic impurity) that forms further to use in the back that is separated.Under situation about being fit to, it can be sold as value product or be used to prepare other product, for example under the situation of sulphite, be used to prepare hyposulfite.For example, sulphite can be the SODIUM HYDROSULPHITE salts solution by electrochemical conversion by for example amalgam or diaphragm process.
Following examples have been set forth the present invention.
Embodiment
Embodiment 1
The crystallization V-Brite B and the formalin solution reaction that contain exogenous salt form NaHMS
In stirring tank, with the crystallization V-Brite B (BASF AGHydrosulfite, surplus exogenous salt) of 880g 88%, promptly 4.5 moles of V-Brite Bs are dissolved in about 3.6L water.Under room temperature, added 4.5 moles of formaldehyde (formalin solution 30% (w/w)) through 20 minutes, stir simultaneously.After adding 4.3 moles of NaOH, by Quantitative yield (online UV spectrum), the pH of solution is 9.7 to V-Brite B.Total has formed 4.31 moles of NaHMS.Based on the hyposulfite meter of initial adding, corresponding NaHMS yield is 95%.
Embodiment 2
The SODIUM HYDROSULPHITE sodium solution (electrolysis effluent liquid) that contains exogenous salt forms HMS with the formalin solution reaction
In stirring tank, add and contain 2.24 moles of V-Brite Bs and 0.6 mole of exogenous salt (NaHSO
3, Na
2SO
3) electrolysis wastewater.The NaOH of adding 50%, adjusting pH is pH＞8 and pH＜10.Under room temperature, added 2.3 moles of formaldehyde (formalin solution 30% (w/w)) subsequently, stir simultaneously through 20 minutes.Adding 50% (w/w) NaOH, is pH=11.5 with final pH regulator.Add the back V-Brite B by Quantitative yield (online UV spectrum).Total has formed 2.21 moles of NaHMS.Based on the hyposulfite meter of initial adding, corresponding NaHMS yield is 98%.
Embodiment 3
Electrodialysis contains the NaHMS aqueous solution of exogenous salt
(electrode is made up of RA2 and expanding metal titanium for Osmota100,5 pairs of ponds, and electrolytic solution is 5% (w/w) Na at electrodialytic cell
2CO
3, cationite CMX, anionite ASV, tunicle CMB) and middle adding reaction soln to be purified, wherein contain 89g/L NaHMS and 116g/L Na in the dilution loop
2SO
3When the operation beginning, very rare salts solution (5.6g/LNaHMS and 10.6g/L Na are contained in the product loop
2SO
3).Under T=35 ℃, apply the electric current of I=1.81A, simultaneously by two loops of pump circulation.After operation, in the dilution loop, there are following concentration: 5.4g/LNaHMS and 120g/L Na
2SO
3Concentration in the product loop is NaHMS and the 27.3g/L Na of 94g/L
2SO
3
Embodiment 4
Methanol extraction contains the NaHMS aqueous solution of exogenous salt
In stirred vessel, in T=40 ℃ mix down total mass m=1401.5g's and contain 0.9 mole of NaHMS and 1.35 moles of Na
2SO
3The aqueous solution and 1401.5gMeOH.After 30 minutes, the crystallization that suction filtration goes out to form.Remaining mother liquor contains 0.876 mole of NaHMS and 0.05 mole of Na
2SO
3
Claims (21)
1. method for preparing-sulfinate with low levels exogenous salt, wherein in pH＞6 time by using the hyposulfite of carbonyl compound or imines reducine metal or alkaline-earth metal or ammonium.
2. the process of claim 1 wherein that pH is 8-13.
3, the process of claim 1 wherein that pH is 9-11.
4, the process of claim 1 wherein and set pH by the oxyhydroxide or the nitrogen base that add basic metal or alkaline-earth metal.
5, claim 1 or 2 method wherein use NaOH to set pH.
6, the process of claim 1 wherein that the mol ratio of the hyposulfite that use and carbonyl compound or group with imine moiety is in the scope of 0.75-1.3.
7, the method for claim 6, wherein the mol ratio of hyposulfite and carbonyl compound or group with imine moiety is in the scope of 0.95-1.05.
8, the method for claim 7, wherein mol ratio is in the scope of 0.99-1.02.
9, claim 1 or 2 method are wherein used the hyposulfite of sodium-salt form.
10, claim 1 or 2 method, wherein carbonyl compound be selected from aliphatic series and aromatics, singly and polyfunctional aldehyde and ketone.
11, claim 1 or 2 method are wherein used derived from NH
3Imines.
12, claim 1 or 2 method, use therein carbonyl compound is a formaldehyde.
13, claim 1 or 2 method wherein prepare hydroxymethanesulfinate.
14, claim 1 or 2 method, use therein hyposulfite are to pass through SO
2Or the electrolytic reduction of sulphite preparation.
15, the process of claim 1 wherein that the-sulfinate product that obtains is further purified by the exogenous salt of removing formation.
16, the method for claim 15 is wherein by using polar water solubleness organic solvent precipitation exogenous salt and separating liquid phase subsequently remove exogenous salt from solid phase.
17, the method for claim 12, wherein solvent is selected from ketone, alcohol, aldehyde, acid amides, sulfoxide, water-soluble cyclic ethers and water-soluble nitrogen-containing heterocycle compound.
18, the method for claim 13, use therein solvent are the alcohol that is selected from methyl alcohol, ethanol and the Virahol.
19, the method for claim 11 is wherein being removed exogenous salt under the influence of electrical gradient or under the influence in pressure gradient.
20, the method for claim 15 wherein applies electrical gradient by electrodialysis or electrophoresis.
21, the method for claim 15 is wherein by infiltration, nanofiltration, reverse osmosis or the specific ion exchanger gradient of exerting pressure.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10355088.7 | 2003-11-24 | ||
| DE2003155088 DE10355088A1 (en) | 2003-11-24 | 2003-11-24 | Production of sulfinate with low extraneous salt content, for use e.g. as reducing agent or radical source in polymerisation, involves reduction of dithionite salt with carbonyl compound or imine under alkaline conditions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1636974A true CN1636974A (en) | 2005-07-13 |
Family
ID=34559736
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410091648 Pending CN1636974A (en) | 2003-11-24 | 2004-11-24 | Process for producing sulfinate with low content exogenous salt |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1561747A3 (en) |
| JP (1) | JP2005154438A (en) |
| CN (1) | CN1636974A (en) |
| DE (1) | DE10355088A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013077855A1 (en) * | 2011-11-22 | 2013-05-30 | Taminco N.V. | Stabilized choline solutions and methods for preparing the same |
| CN102507857B (en) * | 2011-11-22 | 2014-07-16 | 重庆紫光化工股份有限公司 | Method for measuring mass fraction of imine-methyl ether hydrochloride |
| BR112015025267B1 (en) | 2013-04-11 | 2020-11-10 | Taminco | improved process for choline hydroxide |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE172217C (en) * | ||||
| DE180529C (en) * | 1904-10-28 | |||
| US2666075A (en) * | 1950-11-11 | 1954-01-12 | Basf Ag | Process for the production of the dizinc salt of hydroxymethane sulfinic acid |
| DE19743759A1 (en) * | 1997-10-02 | 1999-04-08 | Brueggemann L Kg | New sulfinic acid derivatives, used as reducing agents |
-
2003
- 2003-11-24 DE DE2003155088 patent/DE10355088A1/en not_active Withdrawn
-
2004
- 2004-11-12 JP JP2004329304A patent/JP2005154438A/en not_active Withdrawn
- 2004-11-24 EP EP04027837A patent/EP1561747A3/en not_active Withdrawn
- 2004-11-24 CN CN 200410091648 patent/CN1636974A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP1561747A2 (en) | 2005-08-10 |
| DE10355088A1 (en) | 2005-06-09 |
| JP2005154438A (en) | 2005-06-16 |
| EP1561747A3 (en) | 2006-07-05 |
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| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| AD01 | Patent right deemed abandoned | ||
| C20 | Patent right or utility model deemed to be abandoned or is abandoned |